Apparatus for carrying out chemical reactions



Oct. 26, 1943u F. M. PYzr-:L 1 2,332,527

APPARATUS FOR CARRYING OUT CHEMICAL REACTION Original Filed May 27, 1939 2 Smeets-Sheet 1 rfMpfpAra/e@ 29 @faz/Ame L ,N u 97 j :Am V57 n THAT/N6 Fig. I

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@et 26, 194s. F; M. PYZEL V2,332,527

APPARATUS FOR CARRYING OUT CHEMICAL REACTIONS original Filed May 27, 195s 2 sheets-Sheet 2 70 (OMP/95550,@ mau/v6 36 M50/UM VAPOR/ZE@ MAM-0p m mL V57 lnvemor: Frederic M. Pyle) Patented Oct. 26, 1943 APPARATUS FOB CARRYING OUl` CHEMICAL REACTIONS Frederic M. Pyzel, Piedmont, Calif.

Original application May 27, 1939, Serial No.'

276,251. Divided and this application January 21, 1941, Serial No. 375,210 v 3 Claims.` (Cl. 23-260) This invention relates vto a process of carrying out chemical reactions between reactants in the -fluid state and deals with a novel assemblage of apparatus whereby such reactions may be carried out in a more eiiicient manner. p

An important object of the invention is the provision of .a method and apparatus whereby chemical reactions may be conducted in a more selective manner to produce higher yields of desired end products over longer periods of time and to minimize or suppress undesirable side reactions to a greater extent than hasbeen hitherto attained. It is an, object of my invention to provide a method whereby the proportions of the reactants may be controlled ina simple manner of lgreat flexibility without resort to unnecessary separation of reactionproducts.

Another objectl great sacrifice of the more reactive material pres-V ent due to side reactions thereof. Typical of this class of reactions are the interpolymerization of oleiines of diierent reactivities such; for example, as the reaction of tertiary olefines with secondary olenes to form interpolymers in the presence of v catalysts such as sulfuric and phosphoric acids, i

aluminum chloride, boron fluoride and the like,

and the etheriflcation of unsaturated halides by alcohols in the presence of a base, as the reaction of allyl chloride With-ethyl alcohol and the like in the presence of sodium hydroxide to form ethyl allyl ether in which reaction the tendency of allyl chloride tohydrolyze leads to low yields which greatly increase the cost of the nal product. The esterication of unsaturated and/or of my invention is the provision of apparatus in 'time whereby incomplete or `excessivereaction of one or more components of thereactlon mixture may be avoided. A further object o'f the invention is the provision of a reaction system in which thoroughl mixing `of the reactants may be accomplished and uniformity of the reaction mixture may be maintained throughout the reaction period with the minimum expenditure ,of power. My invention provides maximum desired reaction in minimum time giving high throughput or production capacity for a given apparatus.

My invention is adapted to carry out a'wide variety of different chemical reactions particularly between reactive chemicals, in the liquid phase. As examples of the diverse reactions to which my invention may be applied may be mentioned the sulfation or hydration of oleiines, alkylation, for example, of aromatic compounds such as benzene or of naphthenes, the saponification of fats, etc. My invention is broadly applicable to chemical reactions of both organic and inorganic character and is especially adapted for the performance of reactions involving a plurality of liquid phases. A general type of chemical reaction in which the apparatus and method of my invention havevdemonstrated particular advantage over, prior practice is that involving a plurality of reactants of substantially different orders oi reactivities.

In. the past this type of reaction has proven especially difficult to control, and it has been impractical to secure high yields of product without The reaction apparatus of my invention hydroxy acids, as in the preparation of methyl methacrylate, and alkylation of aromatic hydro.- carbons or phenols involving highly reactive alkylation agents, such for example,as olefines, and condensation of ketones of different reactivities to form ketols or unsaturated ketones, particularly the condensation of ketones with more reactive compounds such as aldehydes, are still other examplesv ofy reactions which may be carried out with improved yields by my process and apparatus.l For the purpose of making my invention more clear its application to reactions of these types, particularly the alkylation of isoparains by oleflnes Whether monomeric or polymeric and the interpolymerization of diierent olenes will be used to illustrate the principles involved. It will be understood, however, that this implies no limitation on the invention as my method and apparatus are applicablefto other types of reaction with the same or other materials.A

In reacting oleiines with isoparans in the presence of catalysts such as sulfuric acid or the like, for example, it has been found that the higher reactivity of the olefne leads it to react preferentially with the acid to form sulfonates or monoor di-alkyl sulfates or to react with other molecules of the same or different olene present to form polymers 0r to undergo other undesirable side reactions. 'Ihese side reactions not only reduce the yield of desired alkylation product but also tend to make the acid ineffective as an a1- kylation catalyst. Only by providing .an excess of the less reactive isoparaffln molecules relative to the olene molecules may these undesirable side reactions be suiciently suppressed so that the reaction may be made to gopredominantly'to alkylation and the catalyst protected. Similarly in prior methods of carrying out the interpoly- I amount of reacted mixture.

' as possible in asse,

merizaticn ofnisomeric oleiines such as normal This tendency to form true `polytion in this regard is the provision of residence time increasing means such as time tanks through which the recycling mixture flows and which are posed to bring about this high ratio of normal to iso-ole'ne by using unreacted hydrocarbon separated from the reaction products as part of the feedl to the resistor. My invention provides a simpler, more effective and economical means for maintaining such desirable high` ratio of the'less reactive to more reactive olefine at all times in the reaction whereby undesirable side reactions v of the more reactive oleiine are eliminated. Since the less reactive molecules will be reacted to a lesser degree than the more reactive molecule involved in the reaction, their ratio in the reacted product will always be higher than their ratio in the feed. My apparatus is-designed to take advantage of this fact. It is so constructed that the ratio of reactants in the reactor may be controlled by recycling a predetermined desirable 'This method of operation makes it unnecessary to separate unreacted components from the reacted mixture in order to supply an excess of the less reactive material to the feed and also provides an improved means for maintaining the reaction temperature within anydesired narrow limits. 'I'he latter advantage is achieved by the recycle stream which so increases the mass of liquid circulating that the 3 effect of the reaction onthe total temperature issmall and can therefore be controlled in a simple and emcient manner.

The advantage of separation of reactants cari be appreciated not only from the fact that -smaller and more economical separating means may be used since only ,so much of the reacted mixture need be separated as is required for actual recovery of the product but also from the consideration of the advantages resulting from the saving involved in remixing. The time required to bring two liquids to the p oint ofcomplete mixture is very important particularly where highly reactive maliminating unnecessary provided with dispersing means, preferably perforated plates so spaced and each providing such a degree of turbulence that the desired uniformity of dispersion is maintained from plate to plate throughout the entire reaction period.

f The recycling of reacted mixture to the reaction has been considered undesirable and has been avoided because of the mistaken belief that the difilculties due tolow yield would berincreased by exposing the reaction product to further reaction and thatthe dilution of the reaction mixture by such products would materially reduce the capacity of the reactor. I have found, however, that no such undesirable results are obtained when the apparatus of ,my invention is used. Whereas in prior art practice of continuous reaction between liquid reactants it has been customary to feed the reactants into a mixing zone and continuously withdraw reaction product in equivalent amount, my apparatus and process make it unnecessary to proportion the reactants in the feed in the same ratio as is required for the reaction. Instead, it is possible by my procedure to employ any desired proportion of reactants in the feed and maintain a different desirable proportion in the reactor. In' my method of operation the time of raction is substantially uniform fior all material passing through the reactor. 'Ihis is in marked contrast to prior reaction methods employing mixing tanks agitated by stirrers or the like, in which it is practically iinpossible to either confine `the mixing to a limited region or provideauniform residence time for'all the 'material treated. In my apparatus, however, the feed inlet and product outlet points are separated by residence time increasing means the fiow through which is positive and uniform and conseterials are involved. VIt is often the case that even though reactants may be 'prsent in the proper over-all'l proportions in a mixture non-uniformities of composition within 'the mixture may lead to localized undesirable reactions which tend to y nullify the effect of the proportions of the reactants. Not only does it take longer to achieve a uniform mixture but also morepower is required quently the opportunity for short-circuiting is absent. This more uniform reaction time made possible by my apparatus lcontributes materially to higheryields and improved quality of product through avoidance of incomplete or excessive reaction.

In the drawing Figure I shows, diagrammatically, one assemblage of apparatus which provides e a particularly desirable means for practicing my as the difference inthe volume of two reactants increases. -My invention eliminates such-mixing dimculties by recycling premlxed reaction mixture to provide the necessary excess of less reac- Y I tive material.

Reactions involving a of phases; such.

for example, as interpolymerization and 1 isoundergoing reaction be of as uniform compositionv or'fder that f ull advantage maybe derived from the excess reactant. My apparatusaccomplishes this end by providing for thorough paramn alkylation reactions using olefines in the invention. Figures II and III illustrate advantageous modiflcations which may be-used for temperature control in the system.

Referring to Figure I, pipe line l representa a supply line for one of the reactants being used and pipe line 2 represents a supply line for the other reactant. It will be understood that my process ,and apparatus may be used in carrying out reactions between more than two reactants b'ut only two are necessary to illustrate the process.` 'I'he feed to thel system from, pipe lines i and 2, together with unreacted material recovered from the product and returned to the system by ,pipe line 3 may be passed by line l through a heat exchanger 5. Instead of such heat exchanger it may be advantageous to use some other type of temperature controlling unit such as a heater or cooler supplied .with a temperature 'ing material as shown. The products may be f conducted byline l to a treating unit I9 in which undesirable components, if present, may. be re moved. Such a unit is particularly advantageous for removal' of water, for example, from hydro.- carbon feed where my invention is being applied to the alkylation of isoparaiiins and the like with oleiines in the presence of alkylation catalysts instead of with line 4.

In mixer 8 the components of the feed may be thoroughly mixed by means of suitable agitating devices not shown or the mixing accomplished by turbulent flow of the reactants in the feed lines may be depended upon to secure the desired intimate contact under substantially non-reaction conditions. Product containing unreacted components may if desired be mixed with the feed, advantageously in mixer 8 to which such product may be introduced by line 9; The resulting mixture ows through pipe line I to circulating line II where it is mixed with previously reacted mixture containing catalyst if necessary. Line II connects with circulating means such as pump l2 from which-the mixture passes in a closed circuit through line I3 to residence time increasing means such as time tank I4-back to line Il.

Means for withdrawing material from the circulating mixture, such as line I5 connecting with separator I5 are provided. Where mixtures made up of two liquid phases are obtained, separator I6 may be a stratiiier from which upper layer may be withdrawn by line I1 and lower layerremoved by line I8. As illustrated, the upper layer is assumed to contain the desired product a part of which may be returned by line 9. to mix with the feed while the remainder is conducted by line 20, contingently through heat exchanger 5, to separating means 2I which may be a still or extractor or other suitable device for separating the desired product from unreacted material present therewith. The product may be withdrawn by line 22 and unreacted material returned, for example, by line 3 for mixingwith the feed. Separating means 2l may be'one or more units in which other components, such for example, as inert material and the like, may be separated in addition to the reaction product. The lower phase of the mixture such for example as the catalystused.

: In order to control the Vproportion o'f reacted mixture withdrawn from the circulating streamA by line I'5,'means such, for example, as restricas mixing nozzles 2'1. The circulating means I2 I may also providedesirable intimate mixing. Disin time tanks is perforated plates 28 capable of persing means are also preferably provided in the residence time increasing means I4. A particularly desirable form of dispersing means for use maintaining the desired dispersion of reaction mixture throughout the residence Itime of the mixture in the tank, though other dispersing means maybe used. 1

A temperature controlling'unit 29 provided with fluid passage means may be used for regulating the reaction temperature. Figure' I shows the temperature controlling u nit in a branch of the circulation system from which a part of the circulating mixture is withdrawn by line 30 and returned by line 3l. For regulating the proportion of reaction' mixture flowing through thetemperature controlling unit 29 a suitable device such as restrictionorice 32 may be provided. The

temperature controlling device may be either a heater or cooler as required. Heat transfer therein may be either direct or indirect. For example, heating may be effected electrically or by means of combustion gases or by a heated fluid or the like. Cooling may be accomplished, for example, by circulating cooling fluid in indirect heat transfer relation with the reaction mixture or by evaporation of a part of the mixture or other suitable` means.

Figure II illustrates an arrangement of my novel apparatus in which the temperature controlling unit 29 is in series communication with residence time increasing means I4. Line I3icompletes the closed circuit. Cooling by means of butane is illustrated, the butane being circulated through unit 29 by'means of pump 33, feed line 34, exit line 35, vaporizer 36 and return line 3`;l. Lines 38 and 39 provide for passage of the -v/aporized butane to a compressor not shown nd return of liquefied butane to the system res ectively. It-will be understood that notonlyy may other cooling agents be used but also heating inl stead of cooling may be provided depending upon -`th nature of the reaction being carried out. Elei of the reactionmixture in unit 29 a pressure reducing valve, not shown, is preferably provided in l line 30 and a pump, not shown, may be used for returning unevaporated mixture to the circuit by line 3|.v Such a cooling method mayalso be used in the system illustrated in Figure 1I whether or not the evaporation ,is carried out'atl the same pressure as used for the reaction. In either case thejvaporized material may be sent to a compressor, not shown, where it may be liqueed and tion orifice 26 and valve- 40 may be provided.'.

Where such. a restriction orifice is used, advantage may be taken of its mixing effect and in such a case feed 'line I0 is preferably joined Vto une u just aheadof ariete ze. Additional mixing effect may advantageously be obtained by',

other suitable means forpromoting intimate mixing established in the circuit such, for example,

then added to the feed to the system or injected directly into the mixture in unit 29 as by line 34. Under such circumstances line 35 may serve as an outlet for vapors and may be directly connected to line 38. f y

The following examples illustrate typical applications of the process and apparatus of my invention to the alkylation of isoparains with oleiines.

i Example' I A hydrocarbon mixture containing about 60% of oleilnes preponderantly of six carbon atoms per molecule was reacted withisobutane in an assemblage of apparatus similar to that shown in the drawings, and having a volume of about 400 gallons (exclusive of the separator). At the start of the run the system was half filled with sulfuric acid of about 99% concentration and' isobutane in the liquid phase then run in until the reactor was full. The circulating pump was then started and after thorough emulsiiication of the isobu-I tane and acida mixture of the olefine with isobutane was introduced. a

The oleilne-containing hydrocarbon was fed to the system at a rate of 0.75 gal. per minute with isobutane feed at the rate of 1.0 gallon per minute. Isobutane recovered from the reaction product was recycled at a rate equivalent to 6.0 gallons of isobutane per minute giving a ratio of approximately l` mols of ,isobutane per mol of oleilne in the feed. Reacted mixture of hydrocarbon and acid was recycled at a rate giving an e'ective ratio of isobutane to olene of about 100 to 1.

In a 24 hour period in which a reaction temperature of about 15 C. to 18 C. was maintained,

a weight per cent yield, based on olene-containing hydrocarbon feed, of 152% was obtained. The concentration of acid withdrawn from the system was 94.5%. By this type of treatment it was found that from a cracked gasoline having an A. S. T. M. octane number of 77.2, products of the following properties may -be obtained:

octane No Total product o. se s1. 2 0 to 210 F. cut 0.89 77. 0 210 to 300 F. -cut 0.15 as. 5 0 to 300 F cut @a4 I Example II acted mixture was recycled at a rate givingan effective ratio of isobutane to olenes of about 65. Theconcentration of the withdrawn acid was 94.5%, having been Y reduced from 98% during the reaction. In a typical period during which the reaction temperature was maintained at 15 to 18 C., 1675 gallons or alkymteiproduet were recovered. After correcting for the alkylation due to olene in the 'isobutane supplied, it was found that a yield of about 200% by volume based on the polymer feed had been obtained. A sample of the product showed 76% boiling betweenv 23 C. and 130 C. and having an. octane number of 92.6 and a. bromine number of 0.1.

Y Example III In plant scale operation of my apparatus for interpolymerization of isobutylene with normal butylene by reacting a butane-butylene fraction with sulfuric acid an additional time tank in series with that shown on the drawings was used. With hydrocarbon feed containing an average of j 28.8% of normal butylenes and 18.8% of isobutylene and using sulfuric acid of about 71% initial concentration a yield of polymer of 176% based on the isobutylene input was obtained while consuming only 1.95 pounds of acid (equivalent of 100% mSOI.) per barrel of hydrocarbon reacted or 0.172 pound of acid'per gallon of polymer produced, by using a ratio of recycled reacted mixr ture such that about 8.5 mois of normal butylenes Yare present at the point of feed inlet per mol of isobutylene. Reducing the proportion of reacted mixture recycled to the equivalent of a 6.5 ratio of normal to isobutylene reduced the yield to `163% total polymer while increasing it to give 'power required for maintaining reactants in a thoroughly dispersed condition. This is preferably achieved by using a pump for circulating the recycle stream which does not have to act simultaneously as a mixing device. The power required for producing and maintaining the dispersion may then be imparted by the pump to the recycle stream and converted into dispersion effect at the feed mixing' nozzles and perforated plates in the time tank. It will thus be seen that my apparatus provides for maximum mechanical.

efficiency as well as high chemical and thermal eiiiciencies.

While the invention has been describedin a detailed manner in connection with specific examples, it will be understood that the same principles may be applied with advantage to other reactions and that my invention is capable of wide variation not only with respect to materials which may be reacted but also in regard to the conditions of operation employed. For example, instead of using an immiscible liquid catalytic agent for promoting the desired reaction suitable suspended solid catalytic agents may be used. Instead of the single time tank shown in the drawings a plurality of residence time increasing means of the same or different types may be used.

- Furthermore, such units may be connected in series or in parallel. Also, instead of the single circulating stream of reaction mixture shown a plurality of such circulating streams may advantageously be employed. For example, pipe line 22 may connect with the feed line I of a similar system in which further reaction is carried out with the same or another suitable reactant. In such operation countercurrent contact with catalyst or the like may be achieved by connecting line 24 of the second reactor assemblage with line 25 of the initial reaction system. Alternatively the two systems may be connected through their respective lines 24 and 25 only. It is also :feasible to eliminate separator I6 from one of the systems and to connect them by line l5 feeding either to a line such as I cr 25. It may in certain cases be desirable to provide cooling or other suitable means in pre-mixer 3 in order to discourage undesirable premature reaction. Where the invention is used for the reaction of hydro- 'carbon with acid, for example, it is not essential usually to have complete separation of hydrocarbon from acid before return of the latter to the recycled stream by line 23 but it may be' desirable I claim as my invention: y l' 1. An apparatus for carrying out chemical reactions comprising a time tank having only two openings therein, said openings being at opposite` ends of said tank, spaced perforated plates within said time tank, a conduit of substantially `smaller cross section than said time tank connecting one of said openings with the suction side of a circulating pump. a closed conduit connecting the discharge outlet -of said pump with p the inlet of a cooler, another closed conduit connecting the outlet of said cooler with the other of said openings inthe time tank, said time tank, pump, cooler and connecting conduits forming a Vcircuit which is completely closed except for three pipe connections on the iirst said conduit, a pipe connecting one of said connections with a decantation tank, a pipe joining the bottom of said decantation tank with another of said connections, another pipe connected with said decantation tank for removing liquid products from the system, and means for introducing reactants into the third of said connections located between the first of said connections and-the pump I in said circuit.

A 2. An apparatus for carrying out chemical reactions comprising a time tank having only two openings therein, a conduit of substantially smaller cross section than said time tank connecting one of said openings with the suction side of a circulating pump, a closed conduit connecting the discharge outlet of said pump with the inlet of a cooler, another closed conduit connecting the outlet of said cooler with the other of said openings in the time tank, said time tank,

pump, cooler and connecting conduits forming a circuit which is completely closed except for three pipe connections on the first said conduit, a pipe connecting one of said connections with a decantation tank,f transfer means connecting Ithe decantation tank and the closed circuit for returning separated liquid from said decantation tank to' the-closed circuit, a drawoi pipe con'- nected to said decantation tank for removing another liquid phase from the system, and means for introducing additional fluid material into the closed circuit. j

3. An apparatus for `carrying out chemical reactions comprising an elongated time tank having openings at the opposite ends thereof, spaced plates'within said tank adapted to 'direct the flow of .liquids from one of said openings to the other, a conduit of substantially smaller cross section than said time tank connecting one of said openings with the suction side of a circulating pump, aclosed conduit connecting the discharge outlet of said pump with the inlet of a cooler, another closed conduit connecting the outlet of said cooler with the other of said openings in the time tank, said time tank, pump, coolerkand connecting conduits forming a circuit which is completely closed except for liquid inlet and outlet connections, a

' pipe connecting one of said connectionswith a decantation tank, a pipe joining the bottom of said decantation tank with another of said connections, another drawoif pipe connected to said decantation tank for withdrawing liquid from the system, and means for introducing additional liquid material into the closed circuit.

vFREDERIC M. PYzEL. 

